JPH01149931A - Manufacture of thermoelectric material - Google Patents
Manufacture of thermoelectric materialInfo
- Publication number
- JPH01149931A JPH01149931A JP30738287A JP30738287A JPH01149931A JP H01149931 A JPH01149931 A JP H01149931A JP 30738287 A JP30738287 A JP 30738287A JP 30738287 A JP30738287 A JP 30738287A JP H01149931 A JPH01149931 A JP H01149931A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- type
- thermoelectric material
- group
- molten state
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910001245 Sb alloy Inorganic materials 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 229910021480 group 4 element Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000010409 thin film Substances 0.000 abstract description 7
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000004857 zone melting Methods 0.000 description 2
- 229910002909 Bi-Te Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、低温（７７〜２００＠Ｋ）で高い性能を発揮
するＢ１−５ｂ系熱電材料の製造方法に関し、さらに詳
しくは、ベルチェ効果を利用する電子冷却用モジュール
の脚部材料、あるいはゼーベック効果を利用する冷熱（
源）発電用モジュールの脚部材料などに有用なｐ型Ｂ１
−５ｂ系合金熱電材料のバルク製造法に関するものであ
る。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing B1-5b thermoelectric materials that exhibit high performance at low temperatures (77 to 200 @K), and more specifically, to The leg material of the electronic cooling module to be used, or the cooling energy that utilizes the Seebeck effect (
Source) p-type B1 useful as leg material for power generation modules, etc.
The present invention relates to a method for bulk manufacturing a -5b alloy thermoelectric material.
Ｂ１−５ｂ系合金は低温域で限られた範囲（例えば４．
２’ ＫにおいてＢＬ ９５Ｓ ｂ ５〜Ｂｉ ｓｏｓ
ｂ ２０）で！０．０１５ｅＶ程度のバンドギャップ
を有するｎ型半導体となり、これが低温域で優れたベル
チェ効果を発揮することは広く知られている（例えば、
特公昭３８−１５４２１号公報参照）。B1-5b alloys have a limited range in low temperature range (e.g. 4.
BL 95S b 5 ~ Bi sos at 2'K
b 20)! It is an n-type semiconductor with a bandgap of about 0.015 eV, and it is widely known that it exhibits an excellent Bertier effect at low temperatures (for example,
(See Japanese Patent Publication No. 38-15421).
このｎ型Ｂ１−Ｓｂ合金は、実は真性半導体であり、キ
ャリアとして電子、正孔ともほぼ同数存在する。しかし
、電子の移動度が正孔の移動度に比べて大きいため、ｎ
型伝導となるとされテイル（例えば、Ｔ、 ＡＯＮＯ及
びＳ、 ＡＩＺＡｗＡ”５ｔｕｄｙ ｏｎ Ｔｈｅｒｍ
ａｌ Ｇａｐ ｏｆ’ Ｂ１−８ｂ Ａ１１ｏｙｓ”Ｔ
ｏｋｙｏ ＤｅｎｋＩ Ｕｎｌｖ、参照）。This n-type B1-Sb alloy is actually an intrinsic semiconductor, and has approximately the same number of electrons and holes as carriers. However, since the mobility of electrons is larger than that of holes, n
type conduction and tails (e.g. T, AONO and S, AIZAwA"5tudy on Therm
al Gap of' B1-8b A11oys”T
(see Okyo Denki Unlv).
また、■族元素Ｓｎ、Ｐｂなどを数１１００ｐｐ固溶さ
せた単結晶Ｂ１−５ｂでは、極低温のいわゆる不純物領
域ではｎ型伝導を示すが、温度上昇と共にｎ型へ反転す
るという報告がある（例えば、曾、ＹＩｌｌ及び＾、
Ａａ＋１ｔｈ、 ５ｏｌｉｄ−８ｔａｔｅ Ｅｌｅｃｔ
ｒｏｎｌｃｓ、 １９７２． Ｖｏｌ、１５． Ｐ、１
１４１〜Ｌ１８５参照）。In addition, there is a report that single crystal B1-5b containing several 1,100 pp of group III elements Sn, Pb, etc., exhibits n-type conduction in the so-called impurity region at extremely low temperatures, but reverses to n-type as the temperature rises ( For example, 曛, YIll and ^,
Aa+1th, 5solid-8tate Elect
ronlcs, 1972. Vol, 15. P, 1
141-L185).
従って、極低温から室温近傍までｐ型となるＢ１−８ｂ
系合金は、単結晶製造を目的とするブリッジマン法やゾ
ーンメルティング法では作製不可能であり、ｎ型材料し
か作製できなかったため、従来、電子冷却用モジニール
の脚部材料への実用は行なわれていなかった。Therefore, B1-8b becomes p-type from extremely low temperatures to near room temperature.
This type of alloy cannot be produced by the Bridgman method or zone melting method, which aims to produce single crystals, and only n-type materials can be produced, so it has not been put to practical use in the leg material of Modinyl for electronic cooling. It wasn't.
このような基本的な問題を解決するため、本出願人は、
以下の組成を有し、低温、例えば７７〜２００＠Ｋにお
いて高い性能を発揮するＢ１−５ｂ系熱電材料及びその
製造方法を開発し、既に特許出願している（特願昭６１
−３５３３７号）。In order to solve these basic problems, the applicant
We have developed a B1-5b thermoelectric material that has the following composition and exhibits high performance at low temperatures, e.g. 77 to 200 K, and a method for producing the same, and have already applied for a patent (Patent Application No. 61).
-35337).
（（Ｂ１＋ｏｏ−ｘ Ｓｂｘ ） ＋００−７ Ｅ 寥
１ ｒｏｏ、＋ Ｅ ！ここで、ＥＩは■族又は■族元
素を示し、ＥＩは■・■族元素を示し、Ｘは５〜２０、
ｙは０〜２０．２は０．０５〜１０である。（但し、上
記合金組成を得るには、３５０〜８００℃の温度で完全
に一液相となっている状態から急冷ロール法などを用い
て、強制固溶体を作製しなければならない場合がある。((B1+oo-x Sbx) +00-7 E 寥1 roo, + E!Here, EI represents the ■ group or ■ group element, EI represents the ■/■ group element, X is 5 to 20,
y is 0-20.2 is 0.05-10. (However, in order to obtain the above alloy composition, it may be necessary to create a forced solid solution from a completely one-liquid phase state at a temperature of 350 to 800° C. using a quench roll method or the like.
）
すなわち、上記のＢ１−５ｂ系熱電材料は、Ｂ１−５ｂ
系母合金として真性半導体色なるＢ１ ＋ｏｏ−ｘ Ｓ
ｂｘ （ここで、ｘ−５〜２０）を採用すると共に
、ｐ型ドーパントとして■族又は■族元素を０．０５〜
１０ａｔ％添加し、また、実用に際して熱電材料の性能
を上げるため、必要に応じて■・■族元素を０〜２０ａ
ｔ％添加するものである。なお、ｐ型ドーパントとして
■族元素を添加する場合には、上記■・■族元素を添加
する必要性はない。) That is, the above B1-5b thermoelectric material is B1-5b
B1 +oo-x S, which has an intrinsic semiconductor color as a mother alloy
bx (here, x-5 to 20), and 0.05 to 0.05 to
In addition, in order to improve the performance of thermoelectric materials in practical use, group ■ and ■ elements may be added in the range of 0 to 20 at%.
t% is added. Incidentally, when adding a group (1) element as a p-type dopant, there is no need to add the above-mentioned group (1) and (2) element.
本出願人の開発に係る上記ｐ型Ｂ１−５ｂ合金は、溶融
状態にあるＢ１−Ｓｂ系合金を非平衡相になりうる冷却
速度で凝固させることにより得られる。すなわち、従来
のブリッジマン法やゾーンメルティング法では、ｐ型ド
ーパントが平衡凝固で固溶される量（数１１００ｐｐ程
度）しか添加できないが、前記した本出願人の方法によ
ると、平衡凝固全以上のｐ型ドーパントを添加すること
が可能となり、その結果、従来作製不可能であったｐ型
Ｂ１−８ｂ合金が作製可能となる。The p-type B1-5b alloy developed by the present applicant is obtained by solidifying a B1-Sb alloy in a molten state at a cooling rate that can result in a non-equilibrium phase. In other words, in the conventional Bridgman method and zone melting method, it is possible to add only the amount of p-type dopant that is dissolved in solid solution during equilibrium solidification (approximately several 1100 pp), but according to the above-mentioned method of the present applicant, more than all It becomes possible to add a p-type dopant of 100%, and as a result, it becomes possible to produce a p-type B1-8b alloy, which was previously impossible to produce.
すなわち、前記従来技術の項で説明したように、■族元
素を平衡凝固で数１１００ｐｐ添加されたＢ１−５ｂ合
金は温度上昇と共にｐ→ｎ型へ反転するが、本出願人の
開発した方法に従って、Ｂ ｉ １００−ｘ Ｓ ｂ
ｘ （ｘ −５〜２０）の真性半導体にｐ型ドーパン
トとして■族又は■族元素を０．０５〜１０ａｔ％添加
する二とにより、７７”Ｋ〜室温近傍においてｎ型伝導
を示すＢ１−５ｂ合金が得られる。That is, as explained in the prior art section, the B1-5b alloy to which several 1,100 pp of group II elements are added by equilibrium solidification changes from p to n type as the temperature rises, but according to the method developed by the applicant, , B i 100-x S b
By adding 0.05 to 10 at% of a group II or group III element as a p-type dopant to the intrinsic semiconductor of An alloy is obtained.
しかしながら、前記したｐ型Ｂ１−５ｂ合金組成のなか
には、非平衡相になりうる冷却速度で凝固させることに
より得られる急冷薄膜はｎ型伝導を示すが、該薄膜から
例えば２００℃でホットプレスしてバルクを作製する際
に著しくｐ型性能を損なうものがあった。However, in some of the p-type B1-5b alloy compositions described above, a rapidly quenched thin film obtained by solidifying at a cooling rate that can result in a non-equilibrium phase exhibits n-type conduction; There were some materials that significantly impaired p-type performance during bulk fabrication.
従って、本発明の目的は、低温（例えば７７〜２００’
Ｋ）で高いｐ型′性能を発揮するＢ１−５ｂ系熱電材料
のバルクを製造できる方法を提供することにある。Therefore, the object of the present invention is to
The object of the present invention is to provide a method for producing a bulk B1-5b thermoelectric material exhibiting high p-type performance in K).
本発明によれば、前記目的を達成するため、１（ＢＩ＋
ｏｏ−ｘ Ｓｂ−） ＋ｏｏ−ＦＥ ｅ ｌ ｔｏｏ
−、Ｅ ！（但し、式中Ｅ１は■族又は■族元素を示し
、ＥｌはＩＶ−ＶＩ族元素を示し、Ｘは５〜２０、ｙは
０〜２０．２は０：０５〜１０である。）で示される組
成を持つＢ１−５ｂ系合金を溶融状態より非平衡相とな
りうる冷却速度で凝固させた後、冷間成形することを特
徴とする熱電材料の製造方法が提供される。According to the present invention, in order to achieve the above object, 1(BI+
oo-x Sb-) +oo-FE e l too
-,E! (However, in the formula, E1 represents a group ■ or group ■ element, El represents a group IV-VI element, X is 5 to 20, and y is 0 to 20.2 is 0:05 to 10.) A method for producing a thermoelectric material is provided, which comprises solidifying a B1-5b alloy having the composition shown above at a cooling rate that allows it to form a non-equilibrium phase from a molten state, and then cold forming it.
上記組成のＢ１−５ｂ系合金を溶融状態から非平衡相と
なりうる冷却速度で凝固させて得られる急冷薄膜はｐ型
伝導を示すが、これを冷間加工してバルクとすることに
より、急冷により得られたｐ型Ｂ１−Ｓｂ系合金の性能
を失うことなくバルクを作製できる。The quenched thin film obtained by solidifying the B1-5b alloy with the above composition from a molten state at a cooling rate that allows it to become a non-equilibrium phase exhibits p-type conduction. A bulk can be produced without losing the performance of the obtained p-type B1-Sb alloy.
冷間加工の方法としては、具体的には、（イ）金型等で
冷間成形する、（ロ）大型プレスで５．０００〜２０，
０００気圧で成形する、（ハ）等方的にＣ，Ｉ 、
Ｐ （Ｃｏｌｄ ｌ５ｏｓｔａｔｉｃ Ｐｒｅｓｓ）に
より５．０００〜１０，０００気圧で成形する、などの
方法が採用できる。Specifically, the cold working method includes (a) cold forming with a mold, etc., (b) a large press with a diameter of 5,000 to 20,
Molding at 000 atmospheres, (c) isotropically C,I,
A method such as molding by P (cold static press) at 5,000 to 10,000 atmospheres can be adopted.
以下、本発明の方法について説明すると、まず溶融状態
にある前記組成のＢ１−８ｂ系合金を非平衡相になりう
る冷却速度で凝固させる。Hereinafter, the method of the present invention will be explained. First, the B1-8b alloy having the above composition which is in a molten state is solidified at a cooling rate that allows it to become a non-equilibrium phase.
具体的には、第１図に示すような装置において、溶湯溜
４にＢ１−Ｓｂ系合金３を装填し、高周波コイル２で加
熱し、Ｂ１−５ｂ系合金を溶融状態とする。一方、金属
製ロール１（φ２００關１幅２０關程度）を５００〜４
００Ｏｒｐｍで回転させ、溶湯溜４より不活性ガス圧（
０，５〜４ ｋｇ ／ ｃｊ ）により溶湯をロールに
噴射させて冷却凝固させる。なお、急冷ロール法を用い
なくとも、平衡凝固より多量のｐ型ドーパントを添加で
きる急速凝固の方法（例えば急冷粉末）でｐ型Ｂ１−５
ｂ合金を作製することは可能であろう。また、上記急速
ロール法においては、製造条件をロール回転数５００〜
４０００ｒｐｍ、ガス噴射圧０．５〜４ ｋｇ ／ ｃ
ｄの範囲に設定しないと、良質な急冷膜が得られないの
で、好ましくは上記範囲に設定する。Specifically, in an apparatus as shown in FIG. 1, a B1-Sb alloy 3 is loaded into a molten metal reservoir 4 and heated by a high frequency coil 2 to bring the B1-5b alloy into a molten state. On the other hand, a metal roll 1 (about 200 mm in diameter and 20 mm in width) was
Rotate at 00 rpm, and inert gas pressure (
0.5-4 kg/cj), the molten metal is injected onto a roll and cooled and solidified. In addition, p-type B1-5 can be produced by a rapid solidification method (e.g., rapid cooling powder) that allows addition of a larger amount of p-type dopant than in equilibrium solidification without using the rapid cooling roll method.
It would be possible to make b alloys. In addition, in the above-mentioned rapid roll method, the manufacturing conditions are set at a roll rotation speed of 500 to
4000rpm, gas injection pressure 0.5-4 kg/c
If it is not set within the range d, a good quality quenched film cannot be obtained, so it is preferably set within the above range.
次いで、得られた急冷薄膜を、前記した方法により冷間
成形する。Next, the obtained quenched thin film is cold-formed by the method described above.
なお、前記した組成のＢ１−５ｂ系合金において、■族
元素（ＡｆＩＳＴＮ等）又は■族元素（Ｓｎ、Ｐｂ等）
の添加量が０．０５ａｔ％未満となると室温近傍までｐ
型伝導を示さなくなり、一方上記元素の添加量を１０ａ
ｔ％より多くすることは実用的に不適当である。（実用
的には、キャリア濃度を１０１９〜１０２°程度に制御
する。）また、本発明のｐ型Ｂ１−５ｂ合金には、実用
に際し熱電材料の熱伝導度を下げ、性能向上を図るため
に、ｐ型伝導を損なわない範囲で■φ■族元素（Ｐｂ５
ｅ 、 ＰｂＴｅ等）を添加してもよい。In addition, in the B1-5b alloy with the above-mentioned composition, group II elements (AfISTN, etc.) or group II elements (Sn, Pb, etc.)
When the amount of addition is less than 0.05at%, p
On the other hand, when the amount of addition of the above elements was increased to 10a
It is practically inappropriate to increase the content by more than t%. (Practically speaking, the carrier concentration is controlled to about 1019 to 102°.) In addition, the p-type B1-5b alloy of the present invention has the following properties: , ■φ■ group elements (Pb5
e, PbTe, etc.) may be added.
当然のこと乍ら、■・■族元素は添加しなくてもよい。Of course, it is not necessary to add group ■ and group ■ elements.
■。■族元素の添加量は２０ａｔ％を超えるとＢ１−Ｓ
ｂ系合金としての熱電能が損なわれるため好ましくない
。■. ■If the amount of group elements added exceeds 20 at%, B1-S
This is not preferable because the thermoelectric power as a b-based alloy is impaired.
以下、実施例及び比較例を示して本発明について具体的
に説明する。なお、本発明が下記実施例により何ら限定
されるものでないことはもとよりである。Hereinafter, the present invention will be specifically explained by showing Examples and Comparative Examples. It goes without saying that the present invention is not limited to the following examples.
比較例ｌ
Ｂ１５ｓＳｔ）＋□の組成をもつＢ１−５ｂ合金にｐ型
ドーパントとしてＩｎを０，５ａｔ％添加し、約６００
℃に加熱し、均一な液相状態とした（ｌａｔｍ前後のＡ
ｒ雰囲気中）。この状態より、約１１０００ｒｐで回転
するＣｕ製ロールにガス噴射圧約１．０ｋｇ／ｃ−で溶
湯を噴きつけ、長さ約２０龍、巾約２鰭、厚さ約３０μ
の薄膜を作製した。Comparative Example 1 0.5 at% of In was added as a p-type dopant to a B1-5b alloy having a composition of B15sSt)+□, and approximately 600
℃ to obtain a uniform liquid phase (A around latm)
r atmosphere). From this state, the molten metal is sprayed at a gas injection pressure of about 1.0 kg/c- onto a Cu roll rotating at about 11,000 rpm, and the length is about 20 fins, the width is about 2 fins, and the thickness is about 30 μm.
A thin film was prepared.
得られた薄膜をＡ「雰囲気中で２００℃、５ｋｇ ／
ｃ−でホットプレスし、１０ｃｍ角のバルクを得た。The obtained thin film was heated at 200°C in an atmosphere of A, with a weight of 5 kg/
A 10 cm square bulk was obtained by hot pressing at c-.
ホットプレスに供した薄膜のゼーベック定数αと、ホッ
トプレス後のαを測定したところ、第２図に示す結果が
得られた。When the Seebeck constant α of the thin film subjected to hot pressing and α after hot pressing were measured, the results shown in FIG. 2 were obtained.
比較例２
Ｂｉ−Ｔｅ系市販材（小松エレクトロニクス（株）製）
ｐ型材料の電気伝導度σ及びゼーベック定数αを測定し
たところ、それぞれ第３図及び第４図に示すとおりであ
った。Comparative Example 2 Bi-Te commercially available material (manufactured by Komatsu Electronics Co., Ltd.)
When the electrical conductivity σ and Seebeck constant α of the p-type material were measured, they were as shown in FIGS. 3 and 4, respectively.
実施例１
比較例１と同様の方法で得た急冷膜を２万気圧で冷間成
形し、１０叩角のバルクを得た。この電気伝導度σ及び
ゼーベック定数αを測定したところ、第５図及び第６図
に示すとおりであった。Example 1 A rapidly cooled film obtained in the same manner as in Comparative Example 1 was cold-formed at 20,000 atm to obtain a bulk with a crush angle of 10. When the electrical conductivity σ and Seebeck constant α were measured, the results were as shown in FIGS. 5 and 6.
実施例２
実施例１における２万気圧成形に代えて１万気圧のＣ，
１，Ｐ、成形を行ない、１０ｃｍ角のバルクを得た。こ
の電気伝導度σ及びゼーベック定数αを測定したところ
、実施例１で得られた結果と同様であった。Example 2 Instead of 20,000 atm molding in Example 1, 10,000 atm C,
1.P. Molding was performed to obtain a 10 cm square bulk. When the electrical conductivity σ and Seebeck constant α were measured, the results were similar to those obtained in Example 1.
比較例１の結果を示す第２図から明らかなように、８１
ｓｓＳｂ＋□ ０．５％Ｉｎは熱的に不安定なため、急
冷薄状態では低温域において正のゼーベック定数、すな
わちｐ型の高い熱電性能を示すが、２００℃でホットプ
レスするとゼーベック定数αは著しく損われ、ｎ型とな
ってしまう。As is clear from FIG. 2 showing the results of Comparative Example 1, 81
Since ssSb+□ 0.5%In is thermally unstable, it exhibits a positive Seebeck constant in the low temperature range in the rapidly quenched thin state, that is, high p-type thermoelectric performance, but when hot-pressed at 200°C, the Seebeck constant α significantly decreases. It becomes damaged and becomes n-type.
これに対して、本発明の方法に従って実施例１．２で得
られたｐ型Ｂ１Ｓｂは、第５図及び第６図から明らかな
ように、冷間成形後にも急冷状態のままの高いｐ型熱電
性能を有している。On the other hand, as is clear from FIGS. 5 and 6, the p-type B1Sb obtained in Example 1.2 according to the method of the present invention remained in the quenched state even after cold forming. It has thermoelectric performance.
実施例１及び比較例２の熱電材料の１００゜Ｋにおける
ゼーベック定数α及び電気伝導度σ及び、定常伝熱法で
測定した熱伝導度にの値を下記表−１に示す。The Seebeck constant α and electrical conductivity σ at 100°K of the thermoelectric materials of Example 1 and Comparative Example 2, as well as the thermal conductivity measured by the steady heat transfer method, are shown in Table 1 below.
表−１；１００°Ｋにおける特性の比較熱電材料の性能
は、一般に２＝α２ ・σ／Ｋ（Ｚ：性能指数、α：ゼ
ーベック定数、σ：電気伝導度、Ｋ：熱伝導度）で評価
され、Ｚが多きい程優れた材料である。Table 1: Comparison of properties at 100°K The performance of thermoelectric materials is generally evaluated using 2 = α2 ・σ/K (Z: figure of merit, α: Seebeck constant, σ: electrical conductivity, K: thermal conductivity) The higher the number of Z, the better the material.
上記表−１より、Ｂ１−ＳｂのＺがＢ１−Ｔｅのそれを
上まわっていることがわかる。From Table 1 above, it can be seen that Z of B1-Sb exceeds that of B1-Te.
すなわち、本発明の方法（実施例１．２）により、低温
域！ごおいて、一般に電子冷却に用いられているＢ１−
Ｔｅ素子よりも優れた性能指数Ｚを有するｐ型Ｂ１Ｓｂ
が得られる。That is, by the method of the present invention (Example 1.2), the low temperature range! In addition, B1-, which is generally used for electronic cooling,
p-type B1Sb with better figure of merit Z than Te element
is obtained.
第１図は急冷ロール法を実施するための装置の概略構成
図、第２図は比較例１で得られたＢ１５ｓｓｂ＋２０．
５％Ｉｎ急冷薄急冷ホットプレス後のバルクのゼーベッ
ク定数の温度変化を示すグラフ、第３図はＢ１−Ｔｅ系
市販ｐ型材料の電気伝導度の温度変化を示すグラフ、第
４図はそのゼーベック定数の温度変化を示すグラフ、第
５図は実施例１で得られたＢ１−Ｓｂ素子の電気伝導度
の温度変化を示すグラフ、第６図はそのゼーベック定数
の温度変化を示すグラフである。
１は金属製ロール、２は高周波コイル、３はＢｉ−Ｂｂ
系合金、４は溶湯溜。
第２図
遍 度 （Ｋ）
第３図
？
第４図
第５図
第６図FIG. 1 is a schematic diagram of an apparatus for carrying out the quench roll method, and FIG. 2 is a diagram of the B15ssb+20.
A graph showing the temperature change in the Seebeck constant of the bulk after 5% In quenching, thin quenching, and hot pressing. Figure 3 is a graph showing the temperature change in electrical conductivity of a B1-Te commercially available p-type material. Figure 4 is the Seebeck constant. FIG. 5 is a graph showing the temperature change of the electrical conductivity of the B1-Sb element obtained in Example 1, and FIG. 6 is a graph showing the temperature change of the Seebeck constant. 1 is a metal roll, 2 is a high frequency coil, 3 is Bi-Bb
Series alloy, 4 is a molten metal sump. Figure 2: Degree of variation (K) Figure 3? Figure 4 Figure 5 Figure 6
Claims (4)
０＿０＿−＿ｙＥ＾II＿ｙ｝＿１＿０＿０＿−＿ｚＥ＾
I ＿ｚ（但し、式中Ｅ＾ I はIII族又はIV族元素を示
し、Ｅ＾IIはIV・VI族元素を示し、ｘは５〜２０、ｙは
０〜２０、ｚは０．０５〜１０である。）で示される組
成を持つＢｉ−Ｓｂ系合金を溶融状態より非平衡相とな
りうる冷却速度で凝固させた後、冷間成形することを特
徴とする熱電材料の製造方法。(1) {(Bi_1_0_0_-_xSb_x)_1_
0_0_-_yE^II_y}_1_0_0_-_zE^
I_z (However, in the formula, E^I represents a group III or IV element, E^II represents a group IV/VI element, x is 5 to 20, y is 0 to 20, z is 0.05 to 10) A method for producing a thermoelectric material, which comprises solidifying a Bi-Sb alloy having a composition shown in 10) at a cooling rate capable of forming a non-equilibrium phase from a molten state, and then cold forming the alloy.
とする特許請求の範囲第１項に記載の方法。(2) The method according to claim 1, wherein the cold forming pressure is 5000 atmospheres or more.
とを特徴とする特許請求の範囲第１項に記載の方法。(3) The method according to claim 1, wherein the cold forming pressure is isotropically 5000 atmospheres or more.
Ｓｂ＿ｘ）＿１＿０＿０＿ｚＥ＾ I ＿ｚ（但し、Ｅ＾
I はIV族元素であり、ｘ及びｚは前記のとおり）で示
される組成を持つものであることを特徴とする特許請求
の範囲第１項乃至第３項のいずれかに記載の方法。(4) Bi-Sb alloy (Bi_1_0_0_-_x
Sb_x)_1_0_0_zE^ I _z(However, E^
4. The method according to claim 1, wherein I is a group IV element, and x and z have the composition shown above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30738287A JPH01149931A (en) | 1987-12-07 | 1987-12-07 | Manufacture of thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30738287A JPH01149931A (en) | 1987-12-07 | 1987-12-07 | Manufacture of thermoelectric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01149931A true JPH01149931A (en) | 1989-06-13 |
Family
ID=17968380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30738287A Pending JPH01149931A (en) | 1987-12-07 | 1987-12-07 | Manufacture of thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01149931A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02267239A (en) * | 1989-04-06 | 1990-11-01 | Komatsu Ltd | Thermoelectric material for low temperature use and its manufacture |
| US5313220A (en) * | 1991-05-30 | 1994-05-17 | Conifer Corporation | Low noise integrated MMDS antenna and down converter |
| JPWO2018038146A1 (en) * | 2016-08-26 | 2019-06-24 | 国立研究開発法人産業技術総合研究所 | Thermoelectric material |
-
1987
- 1987-12-07 JP JP30738287A patent/JPH01149931A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02267239A (en) * | 1989-04-06 | 1990-11-01 | Komatsu Ltd | Thermoelectric material for low temperature use and its manufacture |
| JP2729964B2 (en) * | 1989-04-06 | 1998-03-18 | 株式会社小松製作所 | Thermoelectric material for low temperature |
| US5313220A (en) * | 1991-05-30 | 1994-05-17 | Conifer Corporation | Low noise integrated MMDS antenna and down converter |
| JPWO2018038146A1 (en) * | 2016-08-26 | 2019-06-24 | 国立研究開発法人産業技術総合研究所 | Thermoelectric material |
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